Textiles and conditioning compositions therefor



United States TEXTILES AND CONDITEONING COMPOSITHGNS THEREFOR Gerald S. Tompkins, Ardmore, Pa., assignor to American Viscose Corporation, Philadelphia, Pa., a corporation of Delaware N Drawing. Application April 9, 1953 Serial No. 347,849

Claims. c1. 2523.6)

may be twisting, weaving, knitting or other textile fabrieating procedure, or it may even be a subsequent impregnating or coating procedure, or it may be a series of any two or more of the preceding operations. It is a special object of the invention to provide improved compositions adapted to be applied to filamentary bundles of the character of yarn or tow, that is yarn-like or towlike filamentary bundles or aggregates comprising a plurality of discontinuous fibers, such as staple fibers, or continuous filaments, whether the fibers or filaments in such aggregates be twisted or untwisted for the purpose of rendering such bundles or aggregates more amenable to such textile operations as twisting, doubling, weaving, knitting or the like and in a specific instance to render yarn-like bundles whether twisted or untwisted more adaptable to both doubling and impregnation, especially with a rubber or synthetic rubber latex for the purpose of producing cords or fabrics adapted to reinforce rubber products, such as tires. vide a composition and cords impregnated therewith having a high tensile strength as well as a high capacity of wettability adapting such cords to pick up adequate quantities of a rubber latex. Other objects and advantages of the invention will be apparent from the description hereinafter.

it has been discovered that the application of esters of a saturated fatty acid containing at least 16 carbon atoms with a polyhydric alcohol selected from a group consisting of hexahydric alcohols and the anhydro derivatives of such alcohols to yarns, such as of rayon, increases the oven-dry strength of cords produced therefrom. t

However, the presence of such esters on the cord has rendered the treated cords incapable of picking up adequate amounts of a latex to prepare the cord properly for incorporation into rubber goods. Previous attempts at formulations with wetting agents whether of solid or liquid character have resulted in losses in the oven-dry tensile strength of the treated cords when sufiicient wettability has been imparted to the cord to enable adequate pick-up of the latex. Formulations are also known wherein the ester is combined with large quantities of vegetable, animal or mineral oils in conjunction with wetting agents but in all such formulations, the tensile strength has been markedly reduced when adequate wettability and latex dip pick-up have been imparted thereto.

According to the present invention, compositions are provided comprising an ester of the type mentioned above atent A more specific object is to proin which the high oven-dr tensile strengths of the treated cords have been maintained while the wettability and dip pick-up has been rendered adequate for the production of suitably impregnated cords or fabrics for the production of rubber goods such as tires. This has been accomplished by the incorporation with the compositions containing the ester of the type defined above of a small amount of a liquid polydialkyl siloxane hereinafter more particularly defined and sometimes referred to simply as a silicone.

For the purposes of general application, the composition may be made up in the form of an emulsion in water comprising from 0.1 to 1% of the ester with 0.001' to 0.5% of the liquid silicone defined above and 0.01'to 1% of an emulsifying agent or agents. When the composition is to be applied to a zero twist yarn or one having a negligible twist less than 1% turns per inch, it is preferred to include a water-soluble or dispersible binder or colloid in an amount from 0.2 to 2%.

As the water-soluble or dispersible binding colloid, there may be used polyvinyl alcohol, carboxymethyl cellulose, water-soluble cellulose ethers, such as hydroxyethyl cellulose, and methyl cellulose, and/or copolymers of styrene and fumaric (maleic) acids, (such as the product available under the trade name Stymer), polymethacrylic acid, polyvinyl acetates which have been partially deaeylated sufiiciently to render them water-dispersible or preferably water-soluble, also the salts of such copolymers and polymers, gelatine, chromated gelatines, starch, and starch degradation products such as dextrines.

The ester is a hard wax-like solid such as those ob tained by the reaction of asaturated fatty acid having at least 16 carbon atoms of which palmitic and stearic representative with sorbitol, mannitol, dulcitol, sorbitan, mannitan, sorbide, mannide or the like. The esters may be either predominantly mono-, di-, tri-esters, or mixtures thereof and should have a melting point above 30 C. Examples of specific esters are sorbitol tetrastearate, sorbitan monopalmitate, mannitan monopalmitate, sorbide dipalmitate, sorbide distearate, and sorbitan monostearate.

Any suitable emulsifying agent may be applied, examples being ethylene oxide modified higher fatty alcohols, such as lauryl alcohol etherified with from 2 to 50' or more oxyethylene units per mol of lauryl alcohol, fatty esters of ethylene oxide derivatives of hexitols or their inner anhydrides such. as those mentioned above used in producing the ester, such derivatives containing from 2 to 50 or more ethylene oxide units per molecule of the hexitol or inner anhydride. Soaps such as sodium or potassium oleate, sodium or potassium stearate, sodium or potassium palmitate or the like may be used. Sulfonated fatty compounds or sulfonated aromatic-aliphatic compounds as well as sulfated higher fatty alcohols may be used. Examples of these are dodecyl naphthalene sulfonate, Gardinol LA (sodium oleyl alcohol sulfate) and Igepon T (ROONCH2CH2SOaNa in which R-CO is the acyl radical derived from oleic acid). Mixtures of the emulsifying agents may be used or if desired a single emulsifying agent can be employed. For certain purposes, it is necessary that the composition be stable to heat; for example, when the composition is applied to yarns to be used in making tire cord, it is necessary that the composition withstand the temperatures required for vulcanization of the rubber. purpose, the soaps, such as sodium oleate, the ethylene oxide derivatives of the higher fatty alcohols, and some of the sulfonates, such as Igepon T above, are particularly suitable.

The liquid silicones that are useful in carrying out For this the invention are the polydialkylsiloxanes wherein the alkyl group has from 1 to 3 carbon atoms, namely methyl, ethyl, isopropyl or propyl. These polydialkylsiloxanes have the following formula:

wherein x is from 80 to 800. These silicones are liquids which are stable and resistant to the temperatures to which the textile fabric is subjected, such as vulcanization temperatures for rubber.

For the purpose of preparing twisted yarns for weaving, additional twisting, knitting or the like, wherein minimum we'tt'ability and strength are not essential, preferred proportions of the several ingredients are as follows:

Percent Ester 0.1'-1 Silicone 0.001-O.5 Emulsifie'r 0.01-1 Water Balance to make 100 The proportions given above define the broad ranges of the several component ingredients of the composition for all general applications. be applied to twisted filamentary bundles, such as yarns having at least 2 twists per inch including'pot-spun rayon yarns, for the purpose of preparing the yarns for the doubling into cords and impregnation of the cords with rubber latex to prepare them for incorporation in reinforced rubber articles such as tires, the preferred ranges of the composition are as follows:

Percent Ester 0.2-0.5 Silicone 0.005-0.5

Emulsifier 0.l-0.3 Water Balance to make 100 Percent Ester 0.1-1 Binder 0.2 Si1icone 0.05-0.5 Emusifier 0.05-0.5 Water Balance to make 100 When the compositions of the present invention are to be applied to yarns which comprises untwisted or negligibly twisted filaments or fibers (that is those having less than 1 /2 turns per inch) for the purpose of preparing such yarns for twisting into cords and imparting to the treated cords adequate wettability to enable the cord to pick up large amounts of latex to prepare them for incorporation in reinforced rubber goods, such as tires, the preferred proportions in the composition are as follows:

Percent Ester 0.2-0.5 Binder 0.2-0.6 Silicone 0.05-0.5 Emulsifier 0.05-0.5 Water Balance to make 100 The composition of the present invention is of wide applicability in the textile industry. It is useful "wherever it is desired to apply a wax-type of finish to textile materials. It may be used, as pointed out above, for sizing yarns for textile operations, such as additional When the composition is to twisting, weaving, knitting or other textile operations, and one of its important characteristics is that it is easily scourable so that the textile structures made from the treated yarns can be subjected to normal scouring operations to remove the conditioning material or finish whenever desired. Because of its ready dispersibility it can be left in the textile structures during dyeing operations without interfering with the uniform dyeing of the structures. During the dyeing operation, the finish may or may not be removed. As pointed out hereinabove, it is of primary importance as a preparatory finish for yarns whether twisted or untwisted to render them amenable to doubling operations to produce tire cord. In this particular use, the maintenance of the maximum or optimum ovcndry tensile strength of the twisted cord carrying the conditioning material in combination with maximum or optimum wettability to facilitate the impregnation of such treated cords with latex is extremely important. Tire cords or the like prepared by the use of this conditioning medium or finish produce tires which have good flex life and in which the reinforcement has maximum tensile strength and adherence to the rubber in the body of the article throughout the life thereof.

The textile structures may comprise filaments or fibers of rayon produced either from viscose, cupramrnonium cellulose, or by the saponification of cellulose esters, such as cellulose acetate; cotton; casein or other protein fibers; cellulose ester fibers, such as those of celluloseacetate; nylon-type materials, such as polyamides; vinyl resins, such as copolymers of vinyl chloride with vinyl acetate or acrylonitrile, copolymers of acrylonitrile with vinyl pyridine, methacrylonitrile, vinyl acetate, vinyl chloride, or mixtures of these monomers, polyethylene; glycol terephthalate; or two mixtures of these different types of fibers, especially to those which comprise a predominant proportion of hydrophilic materials, such as cellulosic materials. The amount of the solid materials left upon the textile structure after impregnation with the dispersion or emulsion and drying thereof upon the structure may vary from about to 3% or more based on the weight of the structure. For the purpose of producing tire cords or other rubber reinforcing structures, the application of from /2 to 1% based on the weight of the textile structure is preferred.

In the following examples which are illustrative of the invention, the proportions are in parts by weight unless otherwise noted.

Example I There were mixed together 5 parts of the condensation product of lauryl alcohol with an ethylene oxide having an average of 4 oxyethylene units per molecule of the alcohol, 5 /2 parts of the condensation product of lauryl alcohol with ethylene oxide having an average of 23 oxyethylene units per molecule of the alcohol, and 89 parts of polydimethylsiloxane having an average molecular weight of about 6600 in which the average value of x in the formula given above is about 90. An emulsion in Water is made by incorporating into 99.45 parts of water 0.05 parts of the mixture containing the silicone, 0.15 parts sodium oleate, and 0.3 parts of sorbitan monopalmitate. An l850-denier, 980-filament regenerated cellulose rayon yarn produced from viscose and having about 2% turns per inch of twist was passed through the above emulsion in a slasher in which approximately 10% stretching was exerted on the yarn, and dried under tension. Approximately /2% by weight of the solid conditioning medium remained upon the dried yarn. Such yarns were given 12 turns per inch twist and then plied together with 12 turns per inch of twist to make a 3936 denier cord. The final oven-dry cord has a tensile strength of 3.07 grams per denier and picked up 7.8% of solids from a 14% solids rubber latex dispersion at room temperature (approximately 25 C.) when the cord was passed through such dispersion at a rate of 98 feet per minute. The product was used as reinforcement for tires.

Example II A composition identical with that of Example I was prepared with the exception that in the aqueous emulsion 0.005 parts of the mixture containing the silicone was incorporated into the emulsion instead of 0.05 parts. An 185 O-denier regenerated cellulose rayon yarn having about 2 /2 twists per inch was impregnated with the composition in a slashing operation as in Example I and the yarn was further twisted and plied to form a cord having a total denier of 3793. The oven-dry cord had a tensile strength of 3.00 grams per denier. The cord was made into a fabric which was impregnated with latex, picking up 6.2% thereof under the conditions of Example I, and made into rubber tires which had good flex life, high strength and durability.

Example III Cotton yarns were passed as a warp through a slasher in the sizing box of which the above emulsion was contained. Upon drying, the yarn retained 3% by weight of the solids contained in the sizing bath. The yarns were woven into fabric and the fabric upon scouring became substantially free of the composition.

Example 1'V An emulsion was made with the following ingredients:

Percent Mannitan diplamitate 0.1 Polydiethylsiloxane having an avcrage molecular weight of 7,000 0.001 Sodium oleate 0.15 Sodium salt of oleyl alcohol sulfate 0.1 Water Balance to make 100 r Yarns of cellulose acetate were passed through this emulsion and picked up approximately /4% based on the weight of the yarn. The y: as were subsequently twisted and fabricated by knitting. The conditioning ma terials were removed readily by scouring.

Example V An emulsion was made with the following ingredients:

' Percent Sorbide monostearate 0.3 Polyvinyl alcohol 0.3 Polydimethylsiloxane having an average molecular weight of 63,000 0.3

I Igepon T (see above) 0.1

Water Balance to make 100 Untwisted continuous filament regenerated cellulose rayon yarns having a denier of 1650 were impregnated by passage through this emulsion and approximately /z% by Weight of the conditioning agent remained after drying.

The yarns were twisted and formed into tire cords as in Example I above. The cords were passed through a rubber latex which was readily picked up in adequate amounts and the impregnated cords were made into tires. Such tires had high flex life, strength and durability.

6 It is to be understood that changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

' I claim:

1. An aqueous emulsion for conditioning textile structures consisting essentially of 0.1 to 1 part by weight of an ester of a saturated fatty acid containing at least 16 carbon atoms with a polyhydric alcohol selected from the group consisting of hexahydric alcohols and the anhydro derivatives of such-alcohols, 0.001 to 0.5 parts by weight of a liquid po-lydialkylsiloxane having the following form- Lllil wherein is an integer having a value of from to 800 and R is selected from the group consisting of methyl, ethyl, isopropyl and propyl, 0.01 to -1 part by weight of an emulsifying agent and sufiicient water to make a total of parts by weight.

2. An aqueous emulsion for conditioning textile structures as defined in claim 1 in which the ester is sorbitau monopalmitate.

3. An aqueous emulsion for conditioning textile structures as defined in claim 1 in which the ester is mannitan monopalmitate.

4. An aqueous emulsion for conditioning textile structures as defined in claim 1 in which the ester is sorbide monostcarate.

5. An aqueous emulsion for conditioning textile structures consisting essentially of 0.2 to 0.5 part by weight of an ester of a saturated fatty acid containing at least 16 carbon atoms with a polyhydric alcohol selected from the group consisting of hexahydric alcohols and the anhydro derivatives or" such alcohols, 0.005 to 0.05 parts by weight of a liquid polydialkylsiloxane having the following formula carbon atoms with a polyhydric alcohol selected from the group consisting of hcxahydric alcohols and the anhydro derivatives of such alcohols, 0.2 to 2 parts by weight of a watevdispersible binder, 0.05 to 0.5 part by weight of a liquid polydialltylsiloxane having the following formula wherein x is an integer having a value of from 80 to 800 and R is selected from the group consisting of methyl, ethyl, isopropyl and propyl, 0.05 to 0.5 part by weight of an emulsifying agent and sufiicient water to make a total of 100 parts by weight.

7. An aqueous emulsion for conditioning textile structures consisting essentially of 0.2 to 0.5 part by weight of an ester of a saturated fatty acid containing at least 16 carbon atoms with a polyhydric alcohol selected from the group consisting of hexahydric alcohols and the anhydro derivatives of such alcohols, 0.05 to 0.5 parts by weight of a liquid polydialkylsiloxane having the following formula and R is selected from the group consisting of methyl,

ethyl, isopropyl and propyl, 0.2 to 0.6 part by weight of a \vater-dispersible colloid material, 0.05 to 0.5 part by weight of an emulsifyling agent and sufiicient water to make a total of 100 parts by weight.

8. A textile structure comprising a filamentary bundle carrying a coating of a conditioning agent consisting essentially of 0.1 to 1 part by weight of an ester of a saturated fatty acid containing at least 16 carbon atoms with a polyhydric alcohol selected from the group consisting of hexahydric alcohols and the anhydro derivatives of such alcohols, 0.001' to 0.5 part by weight of a liquid polydialkylsiloxane having the following formula wherein x is an integer having a value of from 80 to 800 and R is selected from the group consisting of methyl, ethyl, isopropyl and propyl, and 0.01 to 1 part by weight of an emulsifying agent.

9. A textile structure as defined in claim 8 wherein the ester in the conditioning agent is sorbitan monopalmitate.

10. A textile structure as defined in claim 8 wherein the ester in the conditioning agent in mannitan monopalmitate.

11. A textile structure as defined in claim 8 wherein the ester in the conditioning agent is sorbide monostearatc.

sisting of hexahydric alcohols and the anhydro derivatives of such alcohols, 0.005 to 0.05 part by weight of a liquid polydialkylsiloxane having the following formula wherein at is an integer having a value of from 80 to 800 and R is selected from the group consisting of methyl, ethyl, isopropyl and propyl and 0.1 to 0.3 parts by weight of an emulsifying agent.

13. A textile structure comprising a filamentary bundle carrying a coating of a conditioning agent consisting essentially of 0.1 to 1 part by weight of an ester of a saturated fatty acid containing at least 16 carbon atoms with a polyhydric alcohol selected from the group consisting of hexahydric alcoholsand the anhydro derivatives of such alcohols, 0.2 to 2 part by weight of a Water-dispersible binder, 0.05 to 0.5 part by weight of a liquid polydialkylsiloxane having the following formula Cit wherein x is an integer having a value of from 80 to 800 and R is selected from the group consisting of methyl, ethyl, isopropyl and propyl and 0.05 to 0.5 part by weight of an emulsifying agent.

14. A textile structure comprising a filamentary bundle carrying a' coating of a conditioning agent consisting essentially of 0.2 to 0.5 part by Weight of an ester of a saturated fatty acid containing at least 16 carbon atoms with a polyhydric alcohol selected from the group consisting of hewaahytlric alcohols and the anhydro derivatives of such alcohols, 0.05 to 0.5 part by weight of a liquid polydialkylsiloxane having the following formula wherein at is an integer having a value of from 80 to 800 and R is selected from the group consisting of methyl, ethyl, isopropyl and propyl, 0.2 to 0.6 part by weight of a water-dispersible colloid material, and 0.05 to 0.5 part by weight of an emulsifying agent.

15. The method of increasing the strength and of increasing the wettability and dip pickup of rubber latex of rayon textile structures which includes applying to the rayon textile structure a conditioning agent consisting essentially of 0.1 to 1 part by weight of an ester of a saturated fatty acid containing at least 16 carbon atoms with a polyhydric alcohol selected from the group consisting of hexahydric alcohols and the anhydro derivatives of such alcohols, 0.001 to 0.5 part by weight of aliquid polydialkylsiloxane having the following formula wherein x is an integer having a value of from 80 to 800 and R is selected from the group consisting of methyl, ethyl, isopropyl and propyl, and 0.01 to 1 part by weight of an emulsifying agent.

- References Cited in the file of this patent UNITED STATES PATENTS 

1. AN AQUEOUS EMULSION FOR CONDITIONING TEXTILE STRUCTURES CONSISTING ESSENTIALLY OF 0.1 TO 1 PART BY WEIGHT OF AN ESTER OF A SATURATED FATTY ACID CONTAINING AT LEAST 16 CARBON ATOMS WITH A POLYHYDRIC ALCOHOL SELECTED FROM THE GROUP CONSISTING OF HEXAHYDRIC ALCOHOLS AND THE ANHYDRO DERIVATIVES OF SUCH ALCOHOLS, 0.001 TO 0.5 PARTS BY WEIGHT OF A LIQUID POLYDIALKYLSILOXANE HAVING THE FOLLOWING FORMULA 